Highly Dispersed NiO Clusters Induced Electron Delocalization of Ni-N-C Catalysts for Enhanced CO2 Electroreduction

Hongqiang Li; Kaining Gan; Ran Li; Huawei Huang; Jiabao Niu; Zhipeng Chen; Jian Zhou; Yan Yu; Jieshan Qiu; Xiaojun He

doi:10.1002/adfm.202208622

Highly Dispersed NiO Clusters Induced Electron Delocalization of Ni-N-C Catalysts for Enhanced CO₂ Electroreduction

Hongqiang Li, Kaining Gan, Ran Li, Huawei Huang, Jiabao Niu, Zhipeng Chen, Jian Zhou, Yan Yu, Jieshan Qiu^*, Xiaojun He^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

53 Scopus citations

Abstract

Oxygen-regulated Ni-based single-atom catalysts (SACs) show great potential in accelerating the kinetics of electrocatalytic CO₂ reduction reaction (CO₂RR). However, it remains a challenge to precisely control the coordination environment of NiO moieties and achieve high activity at high overpotentials. Herein, a facile carbonization coupled oxidation strategy is developed to mass produce NiO clusters-decorated NiNC SACs that exhibit a high Faradaic efficiency of CO (maximum of 96.5%) over a wide potential range (−0.9 to −1.3 V versus reversible hydrogen electrode) and a high turnover frequency for CO production of 10 120 h⁻¹ even at the high overpotential of 1.19 V. Density functional theory calculations reveal that the highly dispersed NiO clusters induce electron delocalization of active sites and reduce the energy barriers for *COOH intermediates formation from CO₂, leading to an enhanced reaction kinetics for CO production. This study opens a new universal pathway for the construction of oxygen-regulated metal-based SACs for various catalytic applications.

Original language	English (US)
Article number	2208622
Journal	Advanced Functional Materials
Volume	33
Issue number	1
DOIs	https://doi.org/10.1002/adfm.202208622
State	Published - Jan 3 2023

Bibliographical note

Funding Information:
This work was partly supported by the National Natural Science Foundation of China (Nos. 22108003, 52072002, 51872005, and U2003216); the Natural Science Foundation of Anhui Provincial Education Department (No. KJ2020A0254); the Research Fund for Young Teachers of Anhui University of Technology (No. QZ202007); and the Wanjiang Scholar Program. H.H. thanks for the support from KAUST Global Fellowship Program. The authors would also like to acknowledge the financial support from the Anhui International Research Center of Energy Materials Green Manufacturing and Biotechnology.

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

Keywords

CO electroreductions
coal tar pitch
electron delocalizations
Ni single-atom catalysts
NiO clusters

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Chemistry
Biomaterials
General Materials Science
Condensed Matter Physics
Electrochemistry

Access to Document

10.1002/adfm.202208622

Cite this

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title = "Highly Dispersed NiO Clusters Induced Electron Delocalization of Ni-N-C Catalysts for Enhanced CO2 Electroreduction",

abstract = "Oxygen-regulated Ni-based single-atom catalysts (SACs) show great potential in accelerating the kinetics of electrocatalytic CO2 reduction reaction (CO2RR). However, it remains a challenge to precisely control the coordination environment of NiO moieties and achieve high activity at high overpotentials. Herein, a facile carbonization coupled oxidation strategy is developed to mass produce NiO clusters-decorated NiNC SACs that exhibit a high Faradaic efficiency of CO (maximum of 96.5%) over a wide potential range (−0.9 to −1.3 V versus reversible hydrogen electrode) and a high turnover frequency for CO production of 10 120 h−1 even at the high overpotential of 1.19 V. Density functional theory calculations reveal that the highly dispersed NiO clusters induce electron delocalization of active sites and reduce the energy barriers for *COOH intermediates formation from CO2, leading to an enhanced reaction kinetics for CO production. This study opens a new universal pathway for the construction of oxygen-regulated metal-based SACs for various catalytic applications.",

keywords = "CO electroreductions, coal tar pitch, electron delocalizations, Ni single-atom catalysts, NiO clusters",

author = "Hongqiang Li and Kaining Gan and Ran Li and Huawei Huang and Jiabao Niu and Zhipeng Chen and Jian Zhou and Yan Yu and Jieshan Qiu and Xiaojun He",

note = "Funding Information: This work was partly supported by the National Natural Science Foundation of China (Nos. 22108003, 52072002, 51872005, and U2003216); the Natural Science Foundation of Anhui Provincial Education Department (No. KJ2020A0254); the Research Fund for Young Teachers of Anhui University of Technology (No. QZ202007); and the Wanjiang Scholar Program. H.H. thanks for the support from KAUST Global Fellowship Program. The authors would also like to acknowledge the financial support from the Anhui International Research Center of Energy Materials Green Manufacturing and Biotechnology. Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

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AU - Gan, Kaining

AU - Li, Ran

AU - Huang, Huawei

AU - Niu, Jiabao

AU - Chen, Zhipeng

AU - Zhou, Jian

AU - Yu, Yan

AU - Qiu, Jieshan

AU - He, Xiaojun

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PY - 2023/1/3

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N2 - Oxygen-regulated Ni-based single-atom catalysts (SACs) show great potential in accelerating the kinetics of electrocatalytic CO2 reduction reaction (CO2RR). However, it remains a challenge to precisely control the coordination environment of NiO moieties and achieve high activity at high overpotentials. Herein, a facile carbonization coupled oxidation strategy is developed to mass produce NiO clusters-decorated NiNC SACs that exhibit a high Faradaic efficiency of CO (maximum of 96.5%) over a wide potential range (−0.9 to −1.3 V versus reversible hydrogen electrode) and a high turnover frequency for CO production of 10 120 h−1 even at the high overpotential of 1.19 V. Density functional theory calculations reveal that the highly dispersed NiO clusters induce electron delocalization of active sites and reduce the energy barriers for *COOH intermediates formation from CO2, leading to an enhanced reaction kinetics for CO production. This study opens a new universal pathway for the construction of oxygen-regulated metal-based SACs for various catalytic applications.

AB - Oxygen-regulated Ni-based single-atom catalysts (SACs) show great potential in accelerating the kinetics of electrocatalytic CO2 reduction reaction (CO2RR). However, it remains a challenge to precisely control the coordination environment of NiO moieties and achieve high activity at high overpotentials. Herein, a facile carbonization coupled oxidation strategy is developed to mass produce NiO clusters-decorated NiNC SACs that exhibit a high Faradaic efficiency of CO (maximum of 96.5%) over a wide potential range (−0.9 to −1.3 V versus reversible hydrogen electrode) and a high turnover frequency for CO production of 10 120 h−1 even at the high overpotential of 1.19 V. Density functional theory calculations reveal that the highly dispersed NiO clusters induce electron delocalization of active sites and reduce the energy barriers for *COOH intermediates formation from CO2, leading to an enhanced reaction kinetics for CO production. This study opens a new universal pathway for the construction of oxygen-regulated metal-based SACs for various catalytic applications.

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